Oxyalkylated derivatives of certain solvent soluble phenol-aldehyde resins



Patented Jan. 8, 1952 OXYALKYLATED DERIVATIVES OF CERTAIN SOLVENT SOLUBLE PHE'NOL-ALDEHYDE RESINS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware N Drawing. Application February 16, 1948 Serial No. 8,725. In Venezuela March 7, 1947 6 Claims.

The present invention is concerned with certain new chemical products, compounds, or compositions which have useful application in various arts. It includes methods or procedures for manufacturing said new chemical products, compounds, or compositions, as well as the products. compounds or compositions themselves. Said new materials or substances are hydrophile oxyalkylated phenol-aldehyde resins obtained from oxyalkylation-susceptible, water-insoluble, or-

ganic solvent-soluble, fusible phenol-aldehyde resins derived from certain difunctional phenols as hereinafter described.

The present application is a continuation in part of our co-pending applications Serial Nos. 513,660 and 6 filed January 17, 1944, Serial No. 666,816, filed May 2, 1946, and Serial Nos. 751,620 and 751,623, filed May 31, 1947, all now abandoned.

Although the herein described products have a number of industrial applications, they are of particlular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion. This-specific application is described and claimed in our co-pendin application Serial No. 8,724, filed February 16, 1948, now Patent 2,499,367, granted March 7, 1950. The new products are also useful as wetting, detergent and levelling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of fruit; in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a constituent of soldering flux preparations; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides,- emulsifying agents. as for example, for cosmetics. spray oils, water-repellent textile finishes; as lubricants; etc.

We have found that if solvent-soluble resins are prepared from difunctional (direactive) phenols in which one of the reactive (c or p) positions of the phenol is substituted by a carboalkoxy radical having 2 to 24 carbon atoms. inthe substantial absence of trifunctional phenols, and aldehydes having not over 8 carbon atoms, subsequent oxyalkylation, and specifically oxyethylatlon, yields products of unusual value. provided that oxyalkylation is continued to the degree that hydrophile properties are imparted to the compound. By substantial absence of trifunctional phenols, we mean that such materials may be present only in amounts So small that they do not interfere with the formation of a solvent-soluble resin product and, especially, of a hydrophile oxyalkylated derivative thereof. The actual amounts to be tolerated will, of course. vary with the nature of the other components of the system; but in general the proportion of trifunctional phenols which is tolerable in the conventional resinification procedures illustrated herein is quite small. In experiments following conventional procedure using an acid catalyst in which we have included trifunctional phenols in amounts of from 3% to about 1% or somewhat less, based on the difunctional phenols, we have encountered difficulties in preparing oxyalkylated derivatives of the type useful in the practice of this invention.

One useful type of compound of the invention may be exemplified in an idealized simplification in the following formula:

mommy. rowmlown -I 0(C!H40)MH H C H R I n which, in turn. is considered a derivative of the fusible, organic solvent-soluble resin polymer on on on n H o o n 11 I! I 3 oi n be at least 2; and R is a carboalkoxy radical having at least 2 and not over 24 carbon atoms. These numerical values of n and n" are, 01' course, on a statistical basis.

More particularly, the products are compounds having the following characteristics:

(1) Essentially a polymer, probably linear but not necessarily so, having at least 3 and preferably not over 15 or 20 phenolic or structural units. It may have more.

(2) The parent resin polymer being fusible and organic solvent-soluble as hereinafter described.

(3) The parent resin polymer being free from cross-linking or structure which cross-links during the heating incidenbto, the oxyalkylation procedure to an extent sufiicient to prevent the possession of hydrophile or sub-surface-active or surface-active properties by the oxyalkylated resin. Minor proportions of trl-iunctional phenols sometimes present in commercial phenols are usually harmless.

(4i Each alkyleneoxy group is introduced at the phenolic hydroxyl position except possibly in an exceptional instance where a stable methylol 'group has been formed by virtue of resin manufacture in presence of an alkaline catalyst and in instances in which the organic substituent has a labile or reactive hydrogen atom, which is not suitably blocked prior to oxyalkylation. Such occurrence of a stable methylol radical is the exception rather than the rule, and in any event apparently does not occur when the resin is manufactured in the presence of an acid catalyst, but valuable products are obtained from resins in which the substituent radical is oxyalkylationsusceptible.

.5) The total number of alkyleneoxy radicals introduced must be at least equal to twice the phenolic nuclei.

(6) The number of alkyleneoxy radicals introduced not only must meet the minimum of item above but also must be suiiicient to endow the product with sufficient hydrophile property to have emulsifying properties, or be self-emulsifiable or self-dispersible, or the equivalent as hereinafter described. The invention is concerned particularly with sub-surface-active and surface-active compounds.

(7) Products derived from para-substituted phenols are usually more valuable than products derived from an ortho-substituted phenol. when both are available. This preference is based, not only on the fact that the para-substitutedphenol is usually cheaper, but also where we have been able to make a comparison it appears to be definitely better, for example, as demulsifiers.

We know of no theoretical explanation of the unusual properties of this particular class of compounds and, as a matter of fact, we have not been able to find a satisfactory explanation even after we have prepared and studied several hundred typical compounds.

We have also ,found that the remarkable properties of the parent materials persist in derivatives which bear a simple genetic relationship to the parent material, and in fact to the ultimate resin polymer, for instance, in the products obtained by reaction of the oxyalkylated compounds with low molal monocarboxy acids, high molal monocarboxy acids, polycarboxy acids, or their anhydrides, alpha-chloro monocarboxy acids, epichlorohydrin, etc. The derivatives also preferably must be otbained from oxyalkylated products showing at least the necessary hydrophile properties per se.

The present invention relates to products ob- .tained by the oxyalkylation 01 certain resins,

para nuclear carboalkoxy substituent having 2 to 24 carbon atoms.

Any aldehyde capable of forming a methylol or a substituted methylol group and having not more than 8 carbon atoms is satisfactory, so long as it does not possess some other functional group or structure which will conflict with the resinification reaction or with the subsequent oxyalkylation of the resin, but the use of formaldehyde, in its cheapest form of an aqueous solution, for the production of the resins is particularly advantageous. Solid polymers of formaldehyde are more expensive and higher aldehydes are both less reactive, and are more expensive. Furthermore, the higher aldehydes may undergo other reactions which are not desirable, thus introducing difliculties into the resinification step. Thus acetaldehyde, for example, may undergo an aldol condensation, and it and most of the higher aldehydes enter into self-resinification when treated with strong acids or alkalis. 0n the other hand, higher aldehydes frequently beneficially affect the solubility and fusibiilty of a resin. This is illustrated, for example, by the different characteristics of the resin prepared from paratertiary amyl phenol and formaldehyde on one hand and a comparable product prepared from the same phenolic reactant and heptaldehyde on the other hand. The former, as shown in certain subsequent examples, is a hard, brittle solid, whereas the latter is soft and tacky, and obviously easier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. The employment of furfural requires careful control for the reason that in addition to its aldehydic function, furfural can form condensations by virtue of its unsaturated structure. The production of resins from furiural for use in preparing products for the present process is most conveniently conducted with weak alkaline catalysts and often with alkali metal carbonates. Useful aldehydes, in addition to formaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde, 2-ethylhexana-l, ethylbutyraldehyde. heptaldehyde, and benzaldehyde, furfural and glyoxal. It would appear that the use of glyoxal should be avoided due to the fact that it is tetrafunctional. However, our experience has been that, in resin manufacture and particularly as described herein, apparently only one of the aldehydic functions enters into the resinification reaction. The inability of the other aldehydic function to enter into the reaction is presumably due to steric hindrance. Needless to say, one can use a mixture of two or more aldehydes although usually this has no advantage.

Resins oi the kind which are used as intermediates for the compounds of this invention are obtained with he use of acid catalysts or alkaline catalysts, or without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amines, and quaternary ammonium bases. It is generally accepted that when ammonia and amines are employed as catalysts they enter into the condensation reaction and, in fact, may operdifferent basic materials are employed.

ass-Lee? ate by initial combination with the aldehydic reactant. The compound hexamethylenetetramine illustrates such a combination. In light of these various reactions it becomes difilcult to present any formula which would depict the structure of the various resins prior to oxyalkylation. More will be said subsequently as to thedifference between the use of an alkaline catalyst and an-acid catalyst; even in the use of an alkaline catalyst there is considerable evidence to indicate that the products are not identical where The basic materials employed include not only those previously enumerated but also the hydroxides of the alkali metals, hydroxides of the alkaline earth metals, salts of strong bases and weak acids such as sodium acetate, etc.

Suitable phenolic reactants include the following: methyl salicylate. butyl salicylate, amyl salicylate, octyl salicylate,- nonyl dodecyl salicylate, benzyl salicylate, cyclohexyl salicylate, oleyl salicylate, styryl salicylate, phenoxy ethyl salicylate; p hydroxy ethyl benzoate.

The phenol employed is of the following formula, with the proviso that R is the carboalkoxy substituent located in the 2,4,6 position, again with the provision as to 3 or 3,5 methyl substitution. This is conventional nomenclature.

numbering the various positions in the usual clockwise manner, beginning with the hydroxyl position as one:

The manufacture of thermoplastic phenolaldehyde resins, particularly from formaldehyde and a difunctional phenol, i. e., a phenol in which one of the three reactive positions (2,4,6) has been substituted, is well known. As has been previously pointed out, there is no objection to a methyl radical in the 3 or 5 position.

Thermoplastic or fusible phenol-aldehyde resins are usually manufactured for the varnish trade and oil solubility is of prime importance.

For this reason, common reactants employed are butyla-ted phenols, amylated phenols, phenylphenols, etc. The methods employed in manufacturing such resins are similar to those employed in the manufacture of ordinary phenolformaldehyde resins, in that either an acid or alkaline catalyst is usually employed. The procedure frequently differs from that employed in the manufacture of ordinary phenol-aldehyde resins in that phenol, being water-soluble, reacts readily with an aqueous aldehyde solution without further difficulty, while when a water-insoluble phenol is employed some modification is usually adopted to increase the interfacial surface and thus cause reaction to take place. A common solvent is sometimes employed. Another procedure employs rather severe agitation to create a large interfacial area. Once the reaction starts to a moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted mass and assist in hastening the reaction. We have found it desirable to employ a small proportion of an organic sulfo-acid as a catalyst, either alone or along with a mineral acid like sulfuric or hydrochloric acid. For example, alkylated aromatic sulfonic acids are effectively employed. Since commercial forms of such acids are effectively employed. Since salicyate.

quently liberated during resinification.

commercial forms of such acids are commonly their alkali salts, it is sometimes convenient to use a small quantity of such alkali salt plus a small quantity of strong, mineral acid, as shown in the examples below. If desired, such organic sulfo-acids may be prepared in situ in the phenol employed, by reacting concentrated sulfuric acid with a small proportion of the phenol. In such cases where xylene is used as a solvent and con-v centrated sulfuric acid is employed, some sulfonation of the xylene probably occurs to produce the sulfa-acid. Addition of a solvent such as xylene is advantageous as hereinafter described in detail. Another variation of procedure is to employ such organic sulfo-acids, in the form of their salts. in connection with an alkali-catalyzed resinification procedure. Detailed examples are included subsequently. I

Another advantage in the manufacture of the thermoplastic Or fusible type of resin by the acid catalytic procedure is that, since a difunctional phenol is employed, an excess of an aldehyde, for instance formaldehyde, may be employed without too marked a change in conditions of reaction and ultimate product. There is usually little, if any, advantage, however, in using an excess over and above the stoichiometric proportions for the reason that such excess may be lost and wasted. For all practical purposes the molar ratio of formaldehyde to phenol may be limited to 0.9 to 1.2, with 1.05 as the preferred ratio, or suflicient, at least theoretically, to convert the remaining reactive hydrogen atom of each terminal phenolic nucleus. Sometimes when higher aldehydes are used an excess of aldehydic reactant can be distilled off and thus recovered from the reaction mass. This same procedure may be used with formaldehyde and excess reactant recovered.

When an alkaline catalyst is used the amount of aldehyde, particularly formaldehyde, may be increased over the simple stoichiometric ratio of one-to-one or thereabouts. With the use of alkaline catalyst it has been recognized that considerably increased amounts of formaldehyde may be used, as much as two moles of formaldehyde, for example, per mole of phenol, or even more, with the result that only a small part of such aldehyde remains uncombined or is subse- Structures which have been advanced to explain such increased use of aldehydes are the following:

Such structures may lead to the production of cyclic polymers instead of linear polymers. For this reason, it has been previously pointed out that, although linear polymers have by far the most important significance, the present invention does not exclude resins of such cyclic structures.

Sometimes conventional resinification procedure is employed using either acid or alkaline catalysts to produce low-stage resins. Such resins may be employed as such, or may be altered or converted into high-stage resins, or in any event, into resins of higher molecular weight, by heating along with the employment of vacuum so as to split oil water or formaldehyde, or both. Generally speaking, temperatures employed, particularly with vacuum, may be in the neighborhood of 175 to 250 0., or thereabouts.

It may be well to point out, however, that the amount 01' formaldehyde used may and does usually aflect the length of the resin chain. Increasing the amount of the aldehyde, such as formaldehyde, usually increases the size or molecular weight of the polymer.

In the hereto appended claims there is specifled, among other things, the resin polymer containing at least 3 phenolic nuclei. Such minimum molecular size is most conveniently determined as a rule by cryoscopic method using benzene, or some other suitable solvent, for instance, one of those mentioned elsewhere herein as a solvent for such resins. As a matter of fact, using the procedures herein described or any conventional resinification procedure will yield products usually having definitely in excess of 3 nuclei. In other words, a resin having an average cl 4, 5 or 5 nuclei per unit is apt to be formed asa minimum in resinification, except under certain special conditions where dimerization may occur.

However, if resins are prepared at substantially higher temperatures, substituting cymene, tetralin, etc., or some other suitable solvent which boils or refluxes at a higher temperature, instead of xylene, in subsequent examples, and if one doubles or triples the amount of catalyst, doubles or triples the time of refluxing, uses a marked excess 01' formaldehyde or other aldehyde, then the average size of the resin is apt to be distinctly over the above values, for example, it may average '7 to 15 units. Sometimes the expression low-stage resin or low-stage" intermediate is employed to mean a stage having 6 or '7 units or even less. In the appended claims we have used low-stage" to mean 3 to 7 units based on average molecular weight.

The molecular weight determinations, of course, require that the product be completely soluble in the particular solvent selected as, for instance, benzene. The molecular weight determination of such solution may involve either the freezing point as in the cryoscopic method, or, less conveniently perhaps, the boiling point in an ebullioscopic method. The advantage of the ebullioscopic method is that, in comparison with the cryoscopic method, it is more apt to insure complete solubility. One such common method to employ is that of Menzies and Wright (see J. Am. Chem. Soc. 43, 2309 and 2314 (1921)). Any suitable method for determining molecular weights will serve, although almost any procedure adopted has inherent limitations. A good method for determining the molecular weights of resins, especially solvent-soluble resins, is the cryoscopic procedure of Krumbhaar which employs diphenylamine as a solvent (see Coating and Ink Resins," page 157, Reinhold Publishing Co.

Subsequent examples will illustrate the use of an acid catalyst, an alkaline catalyst, and no catalyst. Asiar as resin manufacture per se is concerned, we prefer to use an acid catalyst, and particularly a mixture of an organic sulfo-acid and a mineral acid, along with a suitable solvent, such as xylene, as hereinafter illustrated indetail. However, we have obtained products from resins obtained by use of an alkaline catalyst which were just as satisfactory as those obtained employing acid catalysts. Sometimes a combination of both types of catalysts is used in different stages of resinification. Resins so obtainedare also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. e., those referred to as high-stage resins, are conveniently obtained by subjecting lower molecular weight resins to vacuum distillation and heating. Although such procedure sometimes removes only a modest amount or even perhaps no low polymer, yet it is almost certain to produce further polymerization. For instance, acid catalyzed resins obtained in the usual manner and having a molecular weight indicating the presence of approximately 4 phenolic units or thereabouts may be subjected to such treatment, with the result that one obtains a resin having approximately double this molecular weight. The usual procedure is to use a secondary step, heating the resin in the presence or absence of an inert gas, including steam, or by use of vacuum.

We have found that under the usual conditions of resinification employing phenols of the kind here described there is little or no tendency to form binuclear compounds, 1. e., dimers resulting from the combination, for example, of two males of a phenol and one mole of formaldehyde, particularly where the substituent is a hydrocarbon radical and contains 4 or 5 carbon atoms. Where the substituent is hydrocarbon and contains 9 carbon atoms or more there is an increased tendency to form a measurable amount of dimers. The cogeneric formation of a relatively small amount of dimers is unimportant and there is no reason to separate the dimers prior to oxyalkylation and use. Among the phenomena observed as a hydrocarbon substituent increases in size are the following:

(1) There is a tendency to form dimers, even when molar equivalents, or an excess of an aldehyde is used.. This is probably related to one or more of the following: (a) decreased reactiveness or sluggishness due to the increased size of the reac t; (b) statistically less opportunity for rea ion because the point of reaction, the reactive hydrogen atom, is diluted through greater molecular area or space; (0) the structure as such may afford decreased opportunity for reaction.

(2) There is an increased tolerance toward trifunctional phenols,

(3) Increasing the size of the side chain, with a hydrocarbon substituent, increases the carbonoxygen ratio of the finished resin and ultimately 'causes greater solubility in hydrocarbon solvents.

Where the substituent is hydrocarbon and has three carbon atoms or less, there is little tendency to form dimers, but certain differences in behavior as compared with phenols having higher hydrocarbon substituents become significant and noticeable. Thus, they have a decreased tolerance toward trifunctional phenols, and more highly reactive, the carbon-oxygen ratio of the finished resin becomes less, ultimately causing decreased solubility in hydrocarbon solvents, and

the tendency to form resins which harden, cure, or cross-link even though the phenol be difunctional increases.

Resins having substituents containing carbon, oxygen and hydrogen in general exhibit behavior paralleling that of the hydrocarbon-substituted phenol resins, in that if the substituent has a hydrocarbon radical of substantial size, as, for

example, in dodecyl salicylate, the behavior of the resin tends to be similar to that of one obtained from a phenol with a higher hydrocarbon substituent, while if the substituent contains no such group, as in methyl salicylate resins, the behavior tends to be similar to that of the resins derived from phenols having lower hydrocarbon substituents.

The preparation of the resins will be illustrated by the following specific examples. The procedure used in preparing the resins is that described in detail in Example lay of our Patent 2,499,365 and reference is made to that patent for the operating technique.

Example 1a Grams Butyl salicylate (2.0 moles) 388 Formaldehyde 37% (2.3 moles) 182 Concentrated HCl Monoalkyl (Cm-C20, principally 012-014) benzene monosulfonic acid sodium salt 2.5 Xylene 200 The same procedure was followed as in Ex.- ample 1a of Patent 2,499,365. The resin was soft, and amber in color.

Example 2a Grams Amyl salicylate (2.0 moles) 416 Formaldehyde 37% (2.3 moles) 182 Concentrated HCl 20 Monoalkyl (Cm-C20, principally 012-014) benzene monosulfonic acid sodium salt 2.5 Xylene 200 The same procedure was followed as in Example la of Patent 2,499,365. The resin was soft and amber in color.

Example 3a Grams Octyl salicylate (2.0 moles) 500 Formaldehyde 37% (2.3 moles) 182 Concentrated HCl Monoalkyl (Cm-C20, principally C12-C14) benzene monosulfonic acid sodium salt 3.0- Xylene 250 The same procedure was followed as in Example la of Patent 2,499,365. The resin was soft, and amber in color.

Example 4a Grams Methylsalicylate, U. S. P. Grade (2.0

moles) 304 Formaldehyde 37% (2.0 moles) 182 Concentrated HCl 20 Monoalkyl (Cm-C20, principally 012-014) benzene monosulfonic acid sodium salt 1.5

Xylene 200 The phenol, formaldehyde and acid catalyst were combined in the resin pot and reacted following the procedure of Example la of Patent 2,499,365. The resulting resin was soft, amber in color and had a tendency to show a very weak hydrophile effect.

Example 5a Example 4a but showed no hydrophile effect The procedure followed was the same as in I The same procedure was followed as in Example 4a, except that the methyl salicylate was whatever.

Example 7a Grams Para-hydroxy ethylbenzoate 156 Formalin (formaldehyde 37%) 88 Oxalic acid (dissolved in 1 part water) 1.6

The reaction time and conditions were the same as in Example la of Patent 2,499,365. except no alkylaryl sulfonate was added. The reacted components were dehydrated by heating at atmospheric pressure between and C. until a hard non-tacky resin was obtained.

0n heating further to a temperature of 250 C. without vacuum and removing a small amount of additional water, there was obtained an almost transparent, very light amber colored resin, which was not only hard but also brittle.

Having obtained a suitable resin of the kind described, such resin is subjected to treatment with a low molal reactive alpha-beta olefin oxide so as to render the product distinctly hydrophile in nature as indicated by the fact that it becomes self-emulsifiable or miscible or soluble in water, or self-dispersible, or has emulsifying properties.

.If the phenol substituent has a reactive hydrogen is oxyalkylated'along with the phenolic hydroxyls.

The olefin oxides employed for oxyalkylation are characterized by the fact that they contain not over 4 carbon atoms and are selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide. Glycide may be, of course, considered as a hydroxy propylene oxide and methyl glycide as a hydroxy butylene oxide. In anyevent, however, all such reactants contain the reactive ethylene oxide ring and may be best considered as derivatives of or substituted ethylene oxides. The solubilizing effect of the oxide is directly proportional to the percentageof oxygen present, or specifically, to the oxygen-carbon ratio.

Inethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methyl glycide, 1:2. In such compounds, the ratio is very favorable to the production of hydrophile or surface-active properties. However, the ratio, in propylene oxide, is 1:3, and in butylene oxide, 1:4. Obviously, such latter two reactants are satisfactorily employed only where the resin composition is such as to make incorporation of the desired property practical. In other cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They are usable in conjunction with the three more favorable alkylene oxides in all cases. For instance, after one or several propylene oxide or butylene oxide molecules have been attached to the resin molecule, oxyalkylation'may be satisfactorily continued using the more favorable members of the class, to produce the desired hydrophile product. Used alone, these two reagents may in some cases fail to produce sufficiently hydrophile derivatives because of their relatively low oxygen-carbon ratios.

react with almost explosive violence and must be handled with extreme care.

The oxyalkylation oi resins of the kind from which the products of the-present invention are prepared is advantageously catalyzed by the presence of an alkali. Useful alkaline catalysts include soaps, sodium acetate; sodium hydroxide, sodium methylate, caustic potash, etc. The amount of alkaline catalyst usually is between 0.2% to 2%. The temperature employed may vary from room temperature to as high as 200 C. The reaction may be conducted with or without pressure, 1. e., from zero pressure to approximately 200 or even 300 pounds gauge pressure (pounds per square inch). In a general way, the method employed is substantially the sameprocedure as used for oxyallwlation of other organic materials having reactive phenolic groups.

It may be necessary to allow for the acidity of a resin in determining the amount of'alkallne catalyst to be added in oxyalkylation. For instance, if a nonvolatile strong acid such w ,su1-' furic acid is used to catalyze the resiniflcjation reaction, presumably after being converted into a sulfonic acid, it may be necessary and is usually advantageous to add an amount'of alkali equal stoichiometrically to such acidity, and include added alkali over and above this amount as the alkaline catalyst.

It is advantageous to conduct the"oxyethyla-,

tion in presence of an inert solvent such as xylene, cymene, decalin. ethylene glycol diethylether, diethyleneglycol diethylether, or the like,"

although with many resins, the oxyalkylation proceeds satisfactorily without a solvent. Since xylene is cheap and may be permitted to be present in the final product used as a demulsifienit.

is our preference to use xylene. This is particularly true in the manufacture of products from;

low-stage resins, i. e., of 3 and up to and including 7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated, the pressure readings of course represent total pressure, that is, the combined pressure due to xylene and also due to ethylene oxide or whatever other oxyalkylating' agent is used. Under such circumstances it may be necessary at times to use substantial pressures to obtain effective results. for instance, pressures up to 300 pounds along with correspondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such as xylene can be elimi-..

nated in either one of two ways: After the in troduction of approximately 2 or 3 moles of ethylene oxide, for example, per phenolic nucleus,

there is a definite drop in the hardness and melt-.

ing point of the resin. At this stage, if xylene or a similar solvent has been added, it can be eliminated by distillation (vacuum distillation if desired) and the subsequent intermediate, being comparatively solt and solvent-free, can be reorganic solvent.

l2 acted further in the usual manner with ethylene oxide or some other suitable reactant.-

Another procedure is to continue the reaction to completion with such solvent present and then eliminate the solvent by distillation in the customa'ry manner.

Another suitable procedure is to use propylene oxideqr butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the powdered resin infpropylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the original resin dissolved in propylene oxide or butylene oxide, or a mixture which in cludes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final product may contain some unreacted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation in any suitable manner.

. Attentionis directed to the fact that the resins herein described must be fusible or soluble in an Fusible resins invariably are soluble in one or more organic solvents such as those mentioned elsewhere herein. It is to be emphasized, however, that the organic solvent employed to indicate or assure that the resin meets this requirement need not be the one used in oxyalkylation. Indeed solvents which are susceptible to oxyalkylation are included in this group 'of organic solvents. Examples of such solvents are alcohols and alcohol-ethers. However, where a resin is soluble in an organic solvent,

there are usually available other organic solvents which are not susceptible to oxyalkylation, useful for the oxyalkylation step. In any event, the organic solvent-soluble resin can be finely powdered, for instance to 100 to 200 mesh, and

- separate molecules.

a slurry or suspension prepared in xylene or the like, and subjected to oxyalkylation. The fact that the resin is soluble in an organic solvent or the fact that it is fusible means that it consists of Phenol-aldehyde resins of the type herein specified possess reactive hydroxyl groups and are oxyalkylation susceptible.

Considerable of what is said immediately hereinafter is concerned with the ability to vary the hydrophile properties of the compounds from minimum hydrophile properties to maximum hydrophile properties. Even more remarkable, and equally diflicult to explain, are the versatility and utility of these compounds as one goes from minimum hydrophile property to ultimate maximum hydrophile property. For instance, minimum hydrophile property may be described roughly as the point where two ethyleneoxy radicals or moderately in excess thereof are introduced per phenolic hydroxyl. Such minimum hydrophile property or sub-surface-activity or minimum surface-activity means that the product shows at least emulsifying properties or self dispersion in cold or even in warm distilled water (15 to 40 C.) in concentrations of 0.5% to 5.0 7r These materials are generally more soluble in coldwater than warm water, and may even be very insoluble in boiling water. Moderately high temperatures aid in reducing the viscosity of the solute under examination. Sometimes if one continues to shake a hot solution, even though cloudy or containing an insoluble phase, one finds that solution takes place to give a homogeneous phase as the mixture cools. Such self-dispersion tests are conducted in the absence of an insoluble solvent.

When the hydrophile-hydrophobe balance is above the indicated minimum (2 moles of ethylene oxide per phenolic nucleus or the equivalent) but insufficient to give a sol as described immediately preceding, then, and in that event hydrophile properties are-indicated by the fact that one can produce an emulsion by having present to 50% of an inert solvent such as xylene. All that one need to do is to have a xylene solution within the range of 50 to 90 parts by weight of oxyalklated derivatives and 50 to 10 parts by weight of xylene and mix such solution with one. two or three times its volume of distilled water and shake vigorously so as to obtain an emulsion which may be of the oil-in-water type or the water-in-oil type (usually the former) but, in any event, is due to the hydrophile-hydrophobe balance of the oxyalkylated derivative. We prefer simply to use the xylene diluted derivatives, which are described elsewhere, for this test rather than evaporate the solvent and employ any more elaborate tests, if the solubility is not sufficient to permit the simple sol test in water previously noted.-

If the product is not readily water soluble it may :be dissolved in ethyl or methyl alcohol, ethylene glycol diethylether, or diethylene glycol diethylether, with a little acetone added if required, making a rather concentrated solution, for instance 40% to 50%, and then adding enough of the concentrated alcoholic or equivalent solution to give the previously suggested 0.5 to 5.0% strength solution. If the product is selfdispersing (i. e., if the oxyalkylated product is a liquid or a liquid solution self -emulsifiable) such sol or dispersion is referred to as at least semistable in the sense that sols, emulsions, or dispersions prepared are relatively stable, if they remain at least for some period of time, for instance 30 minutes to two hours, before showing any marked separation. Such tests are conducted at room temperature (22 0.). Needless to say, a test can be made in presence of an insoluble solvent such as 5% to of xylene, as noted in previous examples. If such mixture, 1. e., containing a water-insoluble solvent, is as least semistable, obviously the solvent-free product would be even more so. Surface-activity representing an advanced hydrophile-hydrophobe balance can also be determined by the use of conventional measurements hereinafter described. One outstanding characteristic property indicating surface-activity in a material is the ability to form a permanent foam in dilute aqueous solution, for example, less than 0.5%, when in the higher oxyalkylated stage, and to form an emulsion in the lower and intermediate stages of oxyalkylation.

Allowance must be made for the presence of a solvent in the final product in relation to the hydrophile properties of the final product. The principle involved in the manufacture oi the herein contemplated compounds of the invention, is based on the conversion of a hydrophobe or non-hydrophile compound or mixture of compounds into products which are distinctly hydrophile, at least to the extent that they have emulsifying properties or are self-emulsifying; that is, when shaken with water they produce stable or semi-stable suspensions, or, in the presence of a water-insoluble solvent, such as xylene, an emulsion. In demulsiflcation, it is sometimes preferable to use a product having markedly en- 14 han'ced hydrophile properties over and above the initial stage of self-emulsifiability, although we have found that with products of the type used herein, most efilcacious'results are obtained with products which do not have phydrophile properties beyond the stage of self-disnersibility.

More highly oxyalkylated resins give colloidal solutions or sols which show typical properties comparable to ordinary surface-active agents. Such conventional surface-activity may be measured by determining the surface tension and the interfacial tension against paraflin oil or the like. At the initial and lower stages of oxy-alkylation, surface-activity is not suitably determined in this same manner but one may employ an emulsification test. Emulsions come into existence as a rule through the presence of a surfaceactive emulsifying agent. Some surface-active emulsifying agents such as mahogany soap may produce a water-in-oil emulsion or an oil-inwater emulsion depending upon the ratio of the two phases, degree of agitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation. the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufficient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-inwater type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a waterin-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufliciently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

In many cases, there is no doubt as to the presence or absence of hydrophile or surface-active characteristics in the products of this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-surface-activity) tests for emulsifying properties or self-dispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin described above wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may mask the point at which a solvent-free product on more dilution in a test tube exhibits self-emulsiflcation. For this reason, if it is, desirable to determine the approximate point where self-emulsification begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylenesolvent and minor proportions of common eiectrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsiflcation test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it t is really .immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

In light of what has been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the ehectiveness of various alkylene oxides, and most particularly of all ethylene oxide, to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide em ployed, as long as it is at least 2 moles per phenolic nucleus, for producing products useful for the practice of this invention. Another variation is the molecular size of the resin chain resulting from reaction between the difunctional phenol and the aldehyde such as formaldehyde. It is well known that the size and nature or structure of the resin polymer obtained varies somewhat with the conditions of reaction, the proportions of reactants, the nature of the catalyst, etc.

Based on molecular weight determinations, most of the resins prepared as herein described, particularly in the absence of a secondary heating step, contain 3 to 6 or 7 phenolic nuclei with approximately 4 /2 or 5 nuclei as an average. More drastic conditions of resinification yield resins of greater chain length. Such more intensive resinification is a conventional procedure and may be employed if desired. Molecular weight, of course, is measured by any suitable procedure, particularly by cryoscopic methods; but using the same reactants and using more drastic conditions of resinification one usually finds that higher molecular weights are indicated by higher melting points of the resins and a tendency to decreased solubility. See what has been said elsewhere herein in regard to a secondary step involving the heating of a resin with or without the use of vacuum.

We have previously pointed out that either an alkaline or acid catalyst is advantageously used in preparing'the resin. A combination of catalysts is sometimes used in two stages; for instance, an alkaline catalyst is sometimes employed in a first stage. followed by neutralization and addition of a small amount of acid catalyst in a second stage. It is generally believed that even in the presence of an alkaline catalyst, .the number of moles of aldehyde, such as formaldehyde, must be greater than the moles of phenol employed in order to introduce methylol groups in the intermediate stage. There is no indication that such groups appear in the final resin if prepared by the use of an acid catalyst. It is possible that such groups may appear in the finished resins prepared solely with an alkaline catalyst; but we have never been able to confirm this fact in an examination of a large number-of resins prepared by ourselves. Our preference, however, is to use an acid-catalyzed resin, particularly employing a formaldehyde-to-phenol ratio of 0.95 to 1.20 and, as far as we have been able to determine, such resins are free from methylol groups. As a matter of fact, it is probable that in acid-catalyzed resinifications, the methylol structure may appear only momentarily at the very beginning of the reaction and in all probability is converted at once into a more complex structure during the intermediate stage.

One procedure which can be employed in the paratively short time, for instance a'few minutes to 2 to 6 hours, but in some instances requires as much as 8 to 24 hours. A useful temperature range is from to 225 C. The completion of the reaction of each addition of ethylene oxide in step-wise fashion is usually indicated by the reduction or elimination of pressure. An amount conveniently used for each addition is generally equivalent to a mole or two moles of ethylene oxide per hydroxyl radical. When the amount of ethylene oxide added is equivalent to approximately 50% by weight of the original resin, a sample is tested for incipient hydrophile properties by simply shaking up in water as is, or after the elimination of the solvent if a solvent is present. The amount of ethylene oxide used to obtain a useful demulsifying agent as a rule varies from 70% by weight of the original resin to as much as fiveor six times the weight of the original resin. In the case of a resin derived from para-tertiary butylphenol, as little as 50% by weight of ethylene oxide may give suitable solubility. With propylene oxide, even a greater molecular proportion is required and sometimes a resultant of only limited hydrophile properties is obtainable. The same is true to even a greater extent with butylene oxide. The hydroxylated alkylene oxides are more effective in solubilizing properties than the comparable compounds in which no hydroxyl is present.

Attention is directed to the fact that in the subsequent examples reference is made to the stepwise addition of the alkylene oxide, such as ethylene oxide. It is understood, of course, there is no objection to the continuous addition of alkylene oxide until the desired stage of reaction is reached. In fact, there may be less of a hazard involved and it is often advantageous to add the allgvlene oxide slowly in a continuous stream and in such amount as to avoid exceeding the higher pressures noted in the various examples or elsewhere.

It may be well to emphasize the fact that when resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, the resultant is a comparatively soft or pitch-like resin at ordinary temperatures. Such resins become comparatively fluid at 110 to 165 C. as a rule, and thus can be readily oxyalkylated, preferably oxyethyllated, without the use of a solvent.

What has been said previously is not intended to suggest that any experimentation is necessary to determine the degree of oxyalkylation, and particularly oxyethylation. What has been said previously is submitted primarily to emphasize the fact that these remarkable oxyalkylated resins having surface activity show unusual properties as the hydrophile character varies from a minimum to an ultimate maximum. One should not underestimate the utility of any of these products in a surface-active or sub-surfaceactive range without tesing them for the purpose in mind, such as demulsification. A few simple laboratory tests which can be conducted in a routine manner will usually give allthe information that is required.

For instance, a simple rule to follow is to prepare a resin having at least three phenolic nuclei and being organic solvent-soluble. Oxyethylate such resin, using the following four ratios of moles of ethylene oxide per phenolic unit equivalent: 2to1; 6to1; to1; and to1. From a sample of each product remove any solvent that may be present, such as xylene. Prepare 0.5% and 5.0% solutions in distilled water, as previously indicated. A mere examination of such series will generally reveal an approximate range of minimum hydrophile character, moderate hydrophile character, and maximum hydrophile character. If the 2 to 1 ratio does not show minimum hydrophile character by test of the solvent-free product, then one should test its capacity to form an emulsion when admixed with xylene or other insoluble solvent. If neither test shows the required minimum hydrophile property, repetition using 2 to 4 moles per phenolic nucleus will serve. Moderate hydrophile character should be shown by either the 6 to 1 or 10 to 1 ratio. Such moderate hydrophile character is indicated by the fact that the sol in distilled water within the previously mentioned concentration range is a permanent translucent sol when viewed in a comparatively thin layer, for instance the depth of a test tube. Ultimate hydrophile character is usually shown at the 15 to 1 ratio test in that adding a small amount of an insoluble solvent, for instance 5% of xylene, yields a product which will give, at least temporarily, a transparent or translucent sol of the kind just described. The formation of a permanent foam, when a 0.5% to 5.0% aqueous solution is shaken, is an excellent test for surface activity. Previous reference has been made to the fact that other oxyalkylating agents may require the use of increased amounts of alkylene oxide. However, if one does not even care to go .to the trouble of calculating molecular weights, one can simply arbitrarily prepare compounds containing ethylene oxide equivalent to about 50% to 75% by weight, for example 65% by weight, of the resin to be oxyethylate'd; a second example using approximately 200% to 300% by weight, and a third example using about 500% to 750% by weight, to explore the range range. All these tests, as stated, are intended to' beroutine tests and nothing more. They are intended to teach a person, even though unskilled in oxyethylation or oxyalkylation, how to prepare in a perfectly arbitrary manner, a series of compounds illustrating the hydrophile-hydrophobe range.

If one purchases a thermoplastic or fusible resin on the open market selected from a suitable number which are avai able, one might have to make certain determinations in order to make the quickest approach to the appropriate oxyalkylation range. For instance, one should know (a) the molecular size, indicating the number of phenolic units; (b) the nature of the aldehydic residue, which is usually CH2; and; (c) the nature of the substituent. With such information one is in substantially the same position as if one had personally made the resin prior to oxyethylation.

For instance, the molecular weight of the internal structural units of the resin of the following over-simplified formula:

OH OH OH H I; i i; C C H H I (n=1 to 13, or even more) is given approximately by the formula: (M01. wt. of phenol -2) plus mol. wt. of methylene or substituted methylene radical. The molecular weight of the resin would-be n times the value for the internal limit plus the values for the terminal units. The left-hand terminal unit of the above structural formula, it will be seen, is identical with the recurring internal unit except'that it has one extra hydrogen. The right-hand terminal unit lacks the methylene bridge element. Using one internal unit of a resin as the basic element, a resins molecular weight is given approximately by taking (n plus 2) times the weight of the internal element. Where the resin molecule has only 3 phenolic nuclei as in the structure shown, this calculation will be in error by several per cent; but as it grows larger, to contain 6, 9, or 12 phenolic nuclei, the formula comes to be more than satisfactory. Using such an approximate weight, one need only introduce. for

example, two molal weights of ethylene oxide or slightly more, per phenolic nucleus, to, produce a product of minimal hydrophile character. Further oxyalkylation gives enhanced hydrophile character. Although we have prepared and tested a large number of oxyethylated products of the type described herein, we have found no instance where the use of less than 2 moles of ethylene oxide per phenolic nucleus gavedesirable products.

The following Examples 1b through 417 are intended to exemplify the production of suitable .oxyalkylation products from resins described above, giving complete details for carrying out the procedure.

Example 2a.

19 Example 1b The acid catalyzed resin derived trom p hydroxy methylbenzoate in the manner of Example 7a was oxyethylated. 100 grams of this resin were dissolved in a mixture of 50 grams of xylene and 50 grams oi diethyleneglycol diethylether. To this mixture was added three grams of sodium methylate. The mixture was placed in an autoclave and'treated with seven successive batches of ethylene oxide. The following table darker color. If the resins are prepared as customarily employed in varnish resin manufacture, Le, a procedure that excludes the presence of oxygen during the resiniflcation and subsequent cooling of the resin, then of course the initial resin is much Fghter in color. We have employed some resins which initially are almost waterwhite and also yield a lighter colored final product.

The same procedure as described above has been applied to a large variety of resins of the kind described previously, including resins ob- The same procedure was followed as in Example lb except that the resin employed was that of Example 111.

Example 3b The same procedure was followed as in Example lb except that the resin employed was that of Example 4b tacky. viscous liquids to hard, high-melting solids. Their color varies from a light yellow through amber, in a deep red or even almost black. In the manufacture of resins, particularly hard resins, as the reaction progresses the reaction mass frequently goes through a liquid state to a sub-resinous or semi-resinous state, often characterized by being tacky or sticky, to a final complete resin. As the resin is subjected to oxyalkylation these same physical changes tend to take place in reverse. If one starts with a solid resin, oxyalkylation tends to make it tacky or semiresinous and further oxyalkylation makes th tackiness disappear and changes the product to a liquid. Thus, as the resin is oxyalkylated it\ decreases in viscosity, that is, becomes more liquid 330 or changes from a solid to a liquid, particularly when it is converted to the water-dispersible or water-soluble stage. The color of the oxyalkylated derivative is usually considerably lighter than the original product from which it is made, varying from a pale straw color to an amber or reddish amber. The viscosity usually varies from that of an oil, like castor oil, to that of a thick viscous sirup. Some products are waxy. The presence of a solvent, such as 15% xylene or the like, thins the viscosity considerably and also reduces the color in dilution. No undue significance need be attached to the color for the reason that if the same compound is prepared in glass tabulates the data in connection with such treatment:

l I Mar Pres EtO Time Max. Remarks as to solubility and Bstch Added Required Temp., C. at 's appearance a H u a 1 0mm 50 0 r 4 162 88 A viscous opaque liquid; some tendoncy to emulsii'y.

2 50 3 150 132 Same as before; more tendency to cmulsify.

3 50 3 150 Viscosity of iiquid reduced; tends to produce a milky emulsion.

4 50 3% 158 Some tendency to stratify but when mixed together was definitely water emuisiilable.

5 50 5 157 130 Non-viscous amber oil clearly homogeneous; gives a milky emulsion.

6 50 5 160 135 Light colored amber oil; reduces an emulsion of reduced mil iness.

7 50 5% 135 Light colored amber oil with even less-miikiness and reasonably satisfactory solution.

Example 21:

tained from mixtures of phenols, and we have found that these oxyalkylated products having the'required hydrophile properties, are all useful. In many cases useful resins were obtained from aldehydes other than formaldehyde, i. e., higher aldehydes having not over 8 carbon atoms. Similarly, some of the resins instead of being obtained by use of acid catalysts were obtained by use of alkaline catalysts or sequential use of both types of catalyst. In some instances the resins were obtained by a process which involved a secondary step of heating alone or under vacuum.

The oxyethylated products, in the presence of the solvent, were liquids varying in viscosity from relative mobility to a viscosity approaching that of castor oil or lightly blown vegetable oils. They varied in color from straw colored or light amber to very dark brownish or reddish colored. It is to be understood that when these products are used for demulsification, it is unnecessary to separate them from the solvent used in their preparation, and ordinarily commercial products will, if intended for demulsification and if prepared with the use of a solvent, be distributed without removal of the solvent, and frequently with the addition of other solvent materials, other agents, etc. However, for uses in which the presence of the solvent is undesirable or a different solvent is desirable, the solvent is readily removed by distillation, and the product obtained in solvent free form, to be used as such, dissolved in another solvent, or the like.

Actually, in considering the ratio of alkylene oxide to add, and we have previously pointed out thatthis can be predetermined using laboratory tests, it is our actual preference from a practical standpoint to make tests on a small pilot plant scale. Our reason for so doing is that we make one run, and only one, and that we have a complete series which shows the progressive effect of introducing theoxyalkylating agent, for instance, the ethyleneoxy radicals. Our preferred procedate is as follows: We prepare a suitable resin,

and in iron, the latter usually has somewhat 75 or for that matter, purchase it in the open market. We employ 8 pounds of resin and 4 pounds of xylene'and place the resin and xylene in a suitable autoclave with an open reflux condenser. We prefer to heat and stir until the solution is complete. We have pointed out that soft resins which a.;e fluid or semi-fluid can be readily prepared in various ways, such as the use of orthotertiary amylphenol, ortho-hydroxydiphenyl, or by the use of higher molecular weight aldehydes than formaldehyde. If such resins are used, a solvent need not be added but may be added as a matter of convenience or for comparison, if desired. We then add a catalyst, for instance, 2% of caustic soda, in the form of a 20% to 30% solution, and remove the water of solution or formation. We then shut oif the reflux condenser and use the equipment as an autoclave only, and oxyethylate until a total of 60 pounds of ethylene oxide have been added, equivalent to 750% of the original resin. We prefer a temperature of about 150 C. to 175 C. We also take samples at intermediate points as indicated in the following table:

surface-active, upon oxyethylation, particularly extensive oxyethylation. It is also obvious that one mayhave a solven-soluble resin derived from a mixture of phenols having present 1 or 2% of a trifunctional phenol which will result in an insoluble rubber at the ultimate stages of oxyethylation but not in the earlier stages. In other words, with resins from some such phenols, addition of 2 or 3 moles ofthe oxyalkylating agent per phenolic nucleus, particularly ethylene oxide, gives a surface-active product which is perfectly satisfactory, while more extensive oxyethylation yields an insoluble rubber, that is, an unsuitable product. It is obvious that this present procedure of evaluating trifunctional phenol tolerance is more suitable than the previous procedure.

Pounds of Ethylene Percentage Oxide Added per 8 pound Batch Oxyethylation to 750% can usually be completed within 30 hours and frequently more quickly.

The samples taken are rather small, for instance, 2 to 4 ounces, so that no correction need be made in regard to theresidual reaction mass. Each sample is divided in two. One-half the sample is placed in an evaporating dish on the steam bath overnight so as to eliminate the xylene. Then 1.5% solutions are prepared from both series of samples, 1. e., the series with xylene present and the series with xylene removed.

Mere visual examination of any samples in solution may be sufficient to indicate hydrophile character or surface activity, 1. e., the product is soluble, forming a colloidal sol, or the aqueous solution foams or shows emulsifying property.

. All these properties are related through adsorption at the interface, for example, a gas-liquid interface or a liquid-liquid interface. If desired,

surface activity can be measured in any one of,

the usual ways using a Du Nouy tensiometer o dropping pipette, or any other procedure fcir measuring interfacial tension. Such tests are conventional and require no further description. Any compound having sub-surface-activity, and all derived from the same resin and oxyalkylated to a greater extent,i. e., those having a greater proportion of alkylene oxide, are included in this invention.

Another reason why we prefer to use a pilot plant test of the kind above described is that we can use the same procedure to evaluate tolerance towards a trifunctional phenol such as hydroxybenzene or metacresol satisfactorily. Previous reference has been made to the fact that one can conduct a laboratory scale test which will indicate whether or not a resin, although soluble in solvent, will yield an insoluble rubbery product, i. e., a product which is neither hydrophile nor It may be well to call attention to one result which may be noted in a long drawn-out oxyalkylation, particularly oxyethylation, which would not appear in a normally conducted re-* action. Reference has been made to cross-linking and its eifect on solubility and also the fact that, if carried far enough, it causes incipient stringiness, then pronounced stringiness, usually followed by a semi-rubbery or rubbery stage. Incipient stringiness, or even pronounced stringiness, or even the tendency toward a rubbery stage, is not objectionable so long as the final product is still hydrophile and at least sub-surface-active. Such material frequently is best mixed with a polar solvent, such as alcohol or the like, and preferably an alcoholic solution is used. The point which we want to make here, however, is this: Stringiness or rubberization at this stage may possibly be the result of etherification. Obviously if a difunctional phenol and an aldehyde produce a non-cross-linked resin molecule and if such molecule is oxyalkylated so as to introduce a plurality of hydroxy1 groups in each molecule, then and in that event if subsequent etherification takes place, one is going to obtain cross-linking inthe same general way that one would obtain cross-linking in other resinification reactions. Ordinarily there is little or no tendency toward etherification during the oxyalkylation step. If it does take place at all, it is only to an insignificant and undetectable degree. However, suppose that a certain weight of resin is treated with an equa1 weight of, or twice its weight of, ethylene oxide. This may be done in a comparatively short time, for instance, at or C. in 4 to 8 hours, or even less. 0n the other hand, if in an exploratory reaction, such as the kind previouslvdescribed, the ethylene oxide were added extremely slowly in order to take stepwise samples, so that the reaction required 4 or 5 times as long to introduce an equal amount of ethylene oxide employing the same tempera-v ture, then etherification might cause stringiness or a suggestion of rubberiness. For this reason if in an exploratory experiment of the kind previously described there appears to be any stringiness or rubberiness, it may be well to repeat. the experiment and reach the intermediate stage of oxyalkylation as rapidly as possible and then proceed slowly byond this intermediate stage. The entire purpose of this modified procedure is to cut down the time 'of reaction so as to avoid etherification if it be caused by the extended time period.

Ordinarily, the oxyalkylation is carried out in autoclaves provided with agitators or stirring devices.' We have found that the speed of the agitation markedly influences the time of reaction. In some cases, the change from slow speed agitation, for example, in a laboratory autoclave agitation with a stirrer opera-ting at a speed of 60 to 200 R. P. M. to high speed agitation, with the stirrer operating at 250 to 350 R. P. M., reduces the time required for oxyalkylatlon by about onehalf to two-thirds. Frequently xylene-soluble products which give insoluble products by procedures employing comparatively slow speed agitation give suitable hydrophile products when produced by similar procedure but with high speed agitation, as a result, we believe of the reduction in the time required with consequent elimination or curtailment of opportunity for curing or etherization Even if the formation of an insoluble product is not involved, it is frequently advantageous to speed up the reaction. thereby reducing production time, by increasing agitating speed. In large scale operations, we have demonstrated that economical manufacturing results from continuous oxyalkylation, that is, an operation in which the all-xylene oxide is continuously fed to the reaction vessel, with high speed agitation, i. e., an agitator operating at 250 to 350 R. P. M. Continuous oxyalkylation, other conditions being the same, is more rapid than batch oxyalkylation, but the later is ordinarily more convenient for laboratory operation.

It may be well to note one peculiar reaction sometimes noted in the course of oxyalkylation, particularly oxyethylation, of the thermoplastic resins herein described. This effect is noted in a case where a thermoplastic resin has been oxyalkylated, for instance, oxyethylated, until it gives a perfectly clear solution, even in the presence of some accompanying water-insoluble solvent such as to of xylene. Further oxyalkylation, particularly oxyethylation, may then yield a product which, instead of giving a clear solution as previously, gives a very milky solution suggesting that some marked change has taken place. One explanation of the above change is that the structural unit indicated in the following way where 811. is a fairly large number, for instance, 10 to 20, decomposes and an oxyalkylated resin representing a lower degree of oxyethylation and a less soluble one, is generated and a cyclic polymer of ethylene oxide is pro duced, indicated thus:

I HCH This fact, of course, presents no difficulty for the reason that oxyalkylation can be conducted in each instance stepwise, Or at a gradual rate, and samples taken at short intervals so as to arrive at a point where optimum surface activity or hydrophile character is obtained if desired; for most uses, this is not necessary and, in fact, may be undesirable.

We do not know to what extent oxyalkylation produces uniform distribution in regard to phenolic hydroxyls present in the resin molecule. In some instances, of course, such distribution can not be uniform for the reason that we have 24 not specified that the molecules of ethylene oxide, for example, be added in multiples of the units present in the resin molecule. This may be illustrated in the following manner:

Suppose the resin happens to have live phenolic nuclei. If a minimum of two moles of ethylene oxide per phenolic nucleus are added, this would mean an addition of 10 moles of ethylene oxide, but suppose that one added 11 moles of ethylene oxide, or 12, or 13, or 14 moles; obviously, even assuming the most. uniform distribution possible, some of the polyethyleneoxy radicals would contain 3 ethyleneoxy units and some would contain 2. Therefore, it is impossible to specify uniform distribution in regard to the entrance of the ethylene oxide or other oxyalkylating agent. For that matter, if one were to introduce 25 moles of ethylene oxide there is no way to be certain that all chains would have 5 units; there might be some having, for example, 4 and 6 units, or for that matter 3 or 7 units. Nor is there any basis for assuming that the number of molecules of the oxyalkylating agent added to each of the molecules of the resin is the same, or different. Thus, where formulae are given to illustrate or depict the oxyalkylated products, distributions of radicals indicated are to be statistically taken. We have, however, included specific directions and specifications in regard to the total amount of ethylene oxide, or total amount of any other oxyalkylating agent, to add.

In regard to solubility of the resins and the oxyalkylated compounds, and for that matter derivatives of the latter, the following should be noted. In oxyalkylation, any solvent employed should be non-reactive to the alkylene oxide employed. This limitation does not apply to solvents used in cryoscopic determinations for obvious reasons. Attention is directed to the fact that various organic solvents may be employed to verify that the resin is organic solvent-soluble. Such solubility test merely characterizes the resin. The particular solvent used in such test may not be suitable for a molecular weight determination and, likewise, the solvent used in determining molecular weight may not be suitable as a solvent during oxyalkylation, For solution of the oxyalkylated compounds, or their derivatives, a great variety of solvents may be employed, such as alcohols, ether alcohols, cresols, phenols, ketones, esters, etc., alone or with the addition of water. Some of these are mentioned hereafter. We prefer the use of benzene or diphenylamine as a solvent in making cryoscopic measurements. The most satisfactory resins are those which are soldble in xylene or the like, rather than those which are soluble only in some other solvent containing elements other than carbon and hydrogen, for instance, oxygen or chlorine. Such solvents are usually polar, semi-polar, or slightly polar in nature compared with xylene, cymene, etc.

Reference to cryoscopic measurement is concerned with the use of benezene or other suitable compound as a solvent. Such method will show that conventional resins obtained, for example, from para-tertiary amylphenol and formaldehyde in presence of an acid catalyst, will have a molecular weight indicating 3, 4, 5 or somewhat greater number of structural units per molecule. If more drastic conditions of resinification are employed or if such low-stage resin is subjected to a vacuum distillation treatment as previously described, one obtains a resin of a distinctly higher molecular weight. Any molecular weight determination used, whether cryoscopic measurement or other- 25 wise, other than the conventional 'cryoscopic one employing benzene, should be checked so as to insure that it gives consistent values on such con ventionalresins as a control. Frequently all that is'necessary to make an approximation of the molecular weight range is to make a comparison with the dimer obtained by chemical combination of two moles of the same phenol, and one mole of the same aldehyde under conditions to insure dimerization. As to the preparation of dimers from substituted phenols, see Carswell, Phenoplasts, page 31. The increased viscosity, resinous character, and decreased solubility, etc., of the higher polymers in comparison with the dimer, frequently are all that is required to establish that the resin contains 3 or more structural units per molecule.

The instant application relates to oxyalkylated resinous compounds or derivatives thereof. It is obvious that the alicyclic analogues derived by nuclear hydrogenation are equally serviceable for many of the purposes described, and particularly for use in cosmetic preparations, as they are free from certain objections inherent in aromatic ma-- terials. In a general way, conversion of the arcmatic material to an alicyclic material follows either one or two procedures: One can hydrogenate the resin in a conventional manner, followed by oxyalkylation of the hydrogenated resin in substantially the same manner as is employed in the case of the non-hydrogenated resin. The second procedure is to hydrogenate the oxyalkylated derivatives rather than the resin itself. As an example of such procedure, reference is made to our copending applications, Serial Nos. 726,201

and 726,204, filed February 3, 1947, both of whichare now abandoned.

We claim:

1. Hydrophile synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide,

propylene oxide, butylene oxide, glycide ,and-

methylglycide, and (B) an oxyalkylation-sus-,

ceptible, fusible, organic solvent-soluble, waterinsoluble, phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula ethylation-susceptible, fusible, organic solventsoluble, water-insoluble phenolaldehyde resin; said'resin being derived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1- to 20;

with the proviso that at least 2 moles of alkylena oxide be introduced for each phenolic nucleus,

2. Hydrophile synthetic products; said hydrophile synthetic products being oxyethylation products of (A) ethylene oxide, and (B) an oxyin which R is a carboalkoxy radical substituted in the 2,4,6 position having at least 2 and not more than 24 carbon atoms; said oxyethylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyl groups of a plurality of divalent radicals havingv the formula (C:H4O)1.; wherein n is a numeral varying from 1 to 20; with the proviso that at least'2 moles of ethylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of said oxyethylated resin in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

3.- Hydrophile synthetic products; said hydrophile synthetic products being oxyethylation products of (A) ethylene oxide, and (B) an oxyethylation-susceptible, fusible, organic solvent-soluble, water-insoluble, low-stage, acidcatalyzed, phenol-formaldehyde resin having an average molecular weight corresponding to at least -3and not over 7 phenolic nuclei per resin molecule and said resin being derived by reaction between a difunctionai monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula in which R is a carboalkcxy radical substituted in the 2,4,6 position and having at least 2 and not more than 24 carbon atoms; said oxyethylated resin being characterized by the introduc- =tion into the resin molecule of a plurality of divalent radicals having the formula (C2H40)n; wherein-n is a. numeral varying from 1 to 20; with the proviso that at least 2 moles of ethylene oxide be introduced for each phenolic nucleus; and .with the final proviso that the hydrophile properties of said oxyethylated resin in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

ii-The product of claim 3 in which the alkyi radical of the carboalkoxy group is butyl.

5. The product of claim 3 in which the alkyl radical of the carboalkoxy group is amyl.

6. The product of claim 3 in which the alkyl radical of the carboalkoxy group is octyl.

MELVIN DE GROOTE. BERNHARD KEISER.

(References on following page) REFERENCES CITED Number Name Date The following references are of record in the 2354541 3061! et Nov. 23, 1948 file of this patent: 2,499-365 De Groote Mar. 7, 1950 Y .499367 De Groote Mar. 7, 1950 Number UNITEDN:nT1:'IES PATENTS Date 5 OTHER RE ENCES 2,040,112 Orthner et a1 May 12, 1936 'ii g ggjg 1114- Chem" August 2,046,318 Brubaker et a1 Jul 7, 1936 2,076,624 De Groom f' 1937 Ems: Chemistry of Synethic Resins, vol. I.

2,178,829 Bruson et a1 Nov. 7, 1939 10 410413? VOL 1559-1566 (1935)- 

1. HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATERINSOLUBLE, PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN TWO; SAID PHENOL BEING OF THE FORMULA 